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THE EFFECT OF 

MANGANESE COMPOUNDS ON SOILS 

AND PLANTS 



A THESIS 

PRESENTED TO THE FACULTY OF THE GRADUATE SCHOOL 
OF CORNELL UNIVERSITY FOR THE DEGREE OF 

DOCTOR OF PHILOSOPHY 



BY 

EUGENE PEYTON DEATRICK 



SEPTEMBER, 1917 



Reprinted from Memoir No. 19, February. 1919, of Cornell University Agricultural 

Experiment Station 



THE EFFECT OF 

MANGANESE COMPOUNDS ON SOILS 

AND PLANTS 



A THESIS 

PRESENTED TO THE FACULTY OF THE GRADUATE SCHOOL 
OF CORNELL UNIVERSITY FOR THE DEGREE OF 

DOCTOR OF PHILOSOPHY 



BY 

EUGENE PEYTON DEATRICK 

M 



SEPTEMBER. 1917 



Reprinted from Memoir No. 19. February, 1919. of Cornell University Agricultural 

Experiment Station 



.^ lev --'•'• 






CONTENTS 

PAGE 

Review of literature 371 

Experiments with water cultures 371 

Experiments with soil cultures 374 

Experiments with soil fungi and bacteria 377 

Summary 378 

Experimental work 379 

Scope of present study 379 

Effect of manganese compounds on wheat seedlings grown in 

water cultures 379 

Effect of manganese compounds on wheat grown in soil 383 

Manganese content of yellow leaves 387 

Relation of manganese to the oxidizing power of soils 388 

Adsorption of manganese 390 

Oxidation by plant roots 393 

Effect of manganese sulfate on soil bacteria 395 

Ammonification 396 

Nitrification 397 

Conclusions 398 

Literature cited 399 



THE EFFECT OF MANGANESE COMPOUNDS ON SOILS AND 

PLANTS 



THE EFFECT OF MANGANESE COMPOUNDS ON SOILS AND 

PLANTS 

E. P. Deatrick 

Experimental evidence has shown that phosphorus, sulfur, potassium, 
calcium, magnesium, iron, carbon, hydrogen, oxygen, and nitrogen are 
essential to the normal growth and development of plants. Other elements, 
including manganese, are almost universally found in soils and plants, 
and this fact has led some investigators to assume that they perform 
important physiological functions. The weight of evidence, however, 
seems to indicate that the benefit following applications of a manganese 
compound to soil is due to its stimulative, indirect action either on the 
plant or on the soil, and manganese is therefore usually designated as 
a catalytic fertilizer. 

The investigation here recorded was undertaken for the purpose of 
acquiring information regarding the specific effect of manganese com- 
pounds in increasing plant growth; in other words, to determine whether 
manganese is a direct plant stimulant, whether it increases the available 
food supply in the soil, or whether both these factors are operative. The 
direct stimulative or deleterious effect of a substance on plant growth 
may be determined by growing the plant to be studied in water cultures 
of a pure nutrient solution. When the same kind of plant is grown in 
soil to which the substance to be studied is added, the effect is usually 
very much modified. In the soil culture the action must be considered 
as the sum of the effects directly and indirectly on soil and plant. 

REVIEW OF LITERATURE 

Experiments with water cultures 

The effects of manganese on plants have been studied by growing 
seedhngs in distilled water alone, and in distilled water to which nutrient 
salts were added. 

Working with the distilled water cultures, investigators have observed 
both stimulative and toxic effects. Loew and Sawa (1902-03)^ found 
that in the presence of manganese in toxic quantities the leaves lose their 

■Dates in parenthesis refer to Literature cited, page 399. 

371 



372 E. P. Deatrick 

turgor and dry up, and no trace of new rootlets is apparent. In a solution 
containing 1000 parts per million of manganese sulfate, the leaves of 
barley plants faded to yellow and then turned brown. These investi- 
gators found also that barley became chlorotic and the roots turned 
brown in solutions containing only small quantities of manganese. 
McCool (1913) noted that a solution containing 15 parts per million 
of manganese in the form of chloride is injurious to field peas, and that 
a solution containing 30 parts per million prevents root growth entirely. 
Miss Brenchley (1914) found that manganese when present in strong 
concentrations exerts a toxic influence on higher plants. 

On the other hand, several investigators have obtained plant stimulation 
in distilled water cultures containing small quantities of manganese. 
Micheels and De Heen (1906) obtained a pronounced stimulation in 
colloidal solutions of manganese. McCallum (1909) reported an accelera- 
tion of tuber formation when potatoes were treated with a solution of 
manganese chloride. Montemartini (1911), altho finding marked differ- 
ences in the sensitiveness of plants, obtained increased growth with all 
plants used in his experiment. McCool (1913) found slight stimulation, 
as shown by length of the roots of pea seedlings, but the leaves showed 
no effect. 

The effects of manganese in solutions containing nutrient salts are 
similar to those obtained with distilled water cultures, but experiments 
show that the nutrients greatly reduce the toxicity of the manganese. 
McCool (1913) found that this reduction of toxicity is proportional to 
the concentration of the nutrient salts. 

According to Miss Brenchley (1914), 

the Rothamsted experiments supported Aso's work on the action of manganese sulphate 
on barley, concentrations of the salt above 1/100,000 having a retarding influence on the 
growth, the roots being coloured brown and the leaves also showing discolouration. At an early 
stage in growth the lower leaves of the plants receiving the most poison began to be flecked 
with brown spots. 

A solution containing 1350 parts per million of nutrient salts and 770 
parts per million of manganese in the form of sulfate, reduced the yield 
31 per cent. A solution containing but 0.01 of this amount of manganese 
developed brown roots after four weeks and reduced the yield 3 per cent. 
In lower concentrations manganese was decidedly stimulative. Aso 
(1902-03) found that manganese stimulated the growth of a number of 
plants. The solutions which he used contained 0.5 per cent of nutrient 



The Effect of Manganese Compounds on Soils and Plants 373 

salts and 0.02 per cent of manganese sulfate in one series, and 0.05 per 
cent of nutrient salts and 0.002 per cent of manganese sulfate in the 
other series. 

Tottingham and Beck (1916) reported increased yields of wheat grown 
in nutrient solutions containing small quantities of manganese chloride. 

Various views are held regarding. the cause of the stimulation on the 
one hand and of the toxicity on the other. Loew and Sawa (1902-03) 
suggest that the stimulation by manganese is related to the oxidation 
of toxic substances within the plant leaf. They assert that certain noxious 
by-products are formed in the leaf, and that in reality sunlight retards 
growth. They state: "It is in the absence of light that growth 
proceeds and the products of the sun's work are chiefly consumed." 
Protoplasm oxidizes the carbohydrates formed, while the noxious by- 
' products, probably members of the benzene group, are oxidized by enzymes, 
whose action is increased by the presence of manganese. 

Many investigators find that the action of enzymes is in some way 
related to the presence of manganese. Kastle (1910) writes at length 
on manganese in its relation to the oxidizing ferments. It has been 
shown by Bertrand, he states, that the oxidizing power of laccase (from 
lucerne) is associated with the manganese content. He regards t-his 
element as the co-ferment, or activator, of laccase, just as hydrochloric 
acid is the co-ferment of pepsin. The oxidation of organic compounds, 
such as hydroquinon, by the oxygen of the air, is accelerated by the 
presence of manganese and varies with the form of the salt, being greater 
with the salts of the organic acids. These salts are " most easily hydro- 
lyzable"; thus, 

R"Mn -\- HOH = /^''Ho + MnO. 

The manganous oxide formed is " spontaneously oxidizable." In this 
oxidation, " molecular oxygen is spHt into two atoms, one of which com- 
bines with the manganous oxide to form the peroxide, the other going to 
oxidize the hydroquinon "; thus, 

MnO + 02 = Mn02 + O, and 
C6H4 (0H)2 + O = C6H4O2 + HOH. 

In the presence of an acid, R"B.2 is unstable and is capable of oxidizing 
more hydroquinon. Thus the manganese salt is regenerated. " Accord- 
ing to this conception the manganese would be the really active element 



374 E. P. Deatrick 

of the oxidase, so far as the activation and transfer of oxygen is con- 
cerned, whereas the acid albuminoid radicle would impart to the ferment 
its other properties, such as its conduct toward heat, solubility, etc.'' 

Manganese has been found to activate animal ferments. Considerable 
work has been done on the oxidizing power of colloidal solutions of 
manganese, which are described by Kastle as artificial ferments. 

The reports of numerous investigators indicate that a relation exists 
between the presence of manganese and the production of chlorophyll. 
Van Dam (1907) states that seeds soaked in a solution of manganese 
sulfate yield plants which develop greener leaves than normally. Jadin 
and Astruc (1912) report that manganese constantly occurs in the ash 
of plants and that the chlorophyll-bearing parts contain the greatest 
proportion of this element. Mameli (1912) found that chlorophyll is 
produced in some of the lower plants only when manganese is added 
to the nutrient media. Pugliese (1913) states that there is an optimum 
ratio for iron and manganese, which he gives as 1:2.5. Maze (1914) 
has described a special type of chlorosis due to the lack of manganese; 
a large amount in the plant also causes chlorosis. Gile (1916) is of the 
opinion that " manganese chlorosis may be due in part to a deficiency of 
iron in the plant, induced by the action of manganese in the plant or 
in the soil, and in part to a direct toxic action of the manganese." Johnson 
(1917) finds that the toxic effect of manganese on pineapples appears 
to be " due to a depression in the assimilation of iron," and has worked 
out a commercially successful method of counteracting the toxic effect 
by supplying iron thru the leaves. 

Experiments with soil cultures 

A large number of experiments are reported in which manganese salts 
have been applied to soil as a fertilizer. The results are somewhat con- 
tradictory. 

Von Feilitzen (1907) found that manganese sulfate did not increase 
the yield of oats perceptibly. Pfeiffer and Blanck (1912), after experi- 
menting with various salts and plants, decided that their results were 
not conclusive. They state that, while increased yields were occasionally 
obtained, the salts of manganese should not be recommended for general 
use as a fertilizer. This opinion is held also by Sullivan and Robinson 
(1913), who advised that manganese should not be used " in any way 



I 



The Effect of Manganese Compounds on Soils and Plants 375 

other than in experimentation and as a fertiUzer complementary to the 
usual chemical fertilizers." Masoni (1916) experimented with several 
manganese salts. Althothe chloride and the sulfate seemed to give 
a certain advantage, he believed the results were too small to indicate 
definitely the specific effect on the growth of the plants tested. Ehren- 
berg and Schultze (1917) state that experiments covering several j^ears 
show that under many sorts of conditions neither a favoring nor an inhibi- 
tory action of manganese compounds on the growth of plants is de- 
monstrable. At the Woburn station, however, Voelcker (1904) observed 
that manganese iodide, applied at the rate of 50 pounds to the acre, was 
very toxic to the growth of barley. 

On the other hand, some surprising results have been obtained from 
the use of manganese salts. Javillier (1908) states that comparatively 
small quantities of this element have been sufficient to increase the yields 
of certain crops from 25 to 50 per cent. He believes there is no doubt 
that manganese compounds, particularly the sulfate, may be used advan- 
tageously as a complementary manure. Loew and Honda (1904-05) report 
an increase of 50 per cent in Cryptomeria japonica from fertilizing with 
ma.nganese sulfate. With the use of the same salt Ray and Pradier (1909) 
were able to increase the yield of apricots 23 per cent. Bartmann (1910) 
cites Marre as having secured an increase of 60 per cent in some crops. 
Numerous other investigators have reported data indicating that man- 
ganese is a fertilizer of decided value. 

A number of investigators, including Nagaoka (1906-08), and Skinner 
and his co-workers (1914, 1916), report data which are apparently con- 
tradictory. Nagaoka (1906-08) reported that in 1902 manganese sulfate 
applied at the rate of 70 pounds to the .acre, increased the yield of rice 
37 per cent; the following year the residual effect was considerable; in 
1904 the season was " exceptionally favorable," but the treated plats 
again surpassed the checks; in 1905 the experiment was repeated, but that 
year the yield was greatly decreased. Skinner and Sullivan (1914) 
reported their work on the action of manganese in soils; they found that 
the growth of wheat was increased when various salts were added to a 
soil described as an unjjrodudive sandy loam, while on a productive loam 
the salts had no stimulating effect. 

Further experiments were reported by Skinner and Reid (1916), who 
state that " in a six-years field test of manganese sulphate used at the 



376 E. P. Deatrick 

rate of 50 pounds per acre on an acid silty clay loam, its effect each year 
was not beneficial to the crops grown." During the following years of 
experimentation the yields of the crops were increased. The soil had been 
found to be very acid, and large quantities of calcium carbonate were applied. 

It appears that the reaction of the soil is a determining factor in the 
action of manganese. Nagaoka (1906-08) notes that the soil increases in 
acidity with the continued application of manganese sulfate. Rousset 
(1909) cites Malpeaux as securing contradictory results with both the 
sulfate and the chloride of manganese, but favorable results with the 
carbonate and the oxide applied in combination with marl. 

Some results have been obtained, however, which point to a decreased 
stimulation when manganese is applied with some form of calcium. 
According to Uchiyama (1907), " A manurial mixture of a nearly neutral 
reaction, exerts the best effect. Manures of decisive alkaline or acidic 
nature on the other hand are not so favorable, since the former interferes 
with the effect of the manganese salt, while the latter are not suitable 
for the growth of most plants." Chittenden (1915-16) observed the same 
effect; he states that in two out of three cases manganese sulfate alone 
increased the yield, while the addition of lime to the manganese sulfate 
decreased the yield. 

Many of the apparently inconsistent reports are explainable when 
complete data regarding the experiment are available. Some of the 
applications are too low. Others, as that of Crochetelle (1913), who 
supplied an excessive amount (2000 pounds to the acre) of manganese 
sulfate to a " calcareous clay," are high yet stimulative. 

References to the change which manganese compounds may undergo 
when added to soils are numerous. Nottin (1912) found that manganese 
is adsorbed like potassium or ammonia, and is precipitated by calcium 
carbonate and organic matter; the demanganization of water by calcium 
carbonate, and the precipitation of manganese found in dolomitized lime- 
stones, indicate that, in alkaline soils at least, the soluble salts of man- 
ganese are changed to oxides. In the soil solution, manganese probably 
occurs in the form of the bicarbonate, as Vincent (1916) concludes. 
Regarding solubility, Masoni (1916) states that the organic acids are 
particularly active in dissolving manganese. He claims that the behavior 
of the carbonates, sulfates, and oxides of manganese may be explained 
as phenomena of hydrolysis and of successive oxidation and reduction. 



The Effect of Manganese Compounds on Soils and Plants 377 

According to Schreiner, Sullivan, and Reid (1910:37), " soils may have 
practically the same amount of manganese and still vary greatly in oxidiz- 
ing power, so oxidation in soils, if due to manganese, depends on the nature 
of the manganese as much as on the amount." The salts of manganese 
added to soils which were low in this element and had " very httle oxidiz- 
ing power," did not increase their power to oxidize aloin. Experiments to 
learn the effect on oxidation of the addition of hydroxy acids and salts to 
manganese compounds in the soil, led these authors to state (page 56 of 
reference cited): "This oxidation appears to be mainly nonenzymotic, 
the result of interaction between inorganic constituents and certain types 
of organic matter. It may also be brought about by organic matter in 
a state of autoxidation and by inorganic oxygen carriers, such as man- 
ganese and iron. Both processes activate oxygen." 

According to SulHvan and Reid (1912:28), " That the catalytic power 
of the soil is correlated to some degree with the manganese content of 
the soil is evident." A comparison of soils of varying manganese content, 
and the failure of the addition of manganese salts to increase the catalytic 
power of soils that were poor catalyzers even tho the content of manganese 
was high, led these investigators to state that factors other than the " total 
amount of manganese must be the determinants." They suggest that 
either the nature of the manganese compound or the nature of the associ- 
ated organic matter is more important than the amount of manganese. 

Experifnents with soil fungi and bacteria 

Altho the experimentation is meager, the weight of evidence supports 
the conclusions of Bertrand (1909) that manganese stimulates the growth 
of fungi. Loew and Sawa (1902-03), however, found no stimulation, and 
they have written at length on the difference of the behavior of manganese 
on the growth of phanerogams. 

Kelley (1912) concluded that nitrification took place more rapidly in the 
soil high in manganese, while ammonification was about equal in soils 
cf either high or low manganese content. Leoncini (1910) and Montanari 
(1914) have found that manganese increases the activity of nitrifying 
bacteria. 

Brown (Brown and Minges, 1916) applied various salts of manganese 
to soil cultures, and concluded from his data that " if manganese salts 
in small quantities increase crop 3delds on a soil, that increase may be 



378 E. P. Deatrick 

due in part at least to a beneficial effect on ammonification and nitrifica- 
tion." If, on the other hand, the salts " restrict crop growth, that restric- 
tion may be due in part to a depression of bacterial activity." 

Greaves (1916) has recently published his results. He states that with 
the possible exception of the chloride, all the manganese salts tested were 
strong stimulants to the ammonifying organisms of the soil. At maxi- 
mum stimulation, 25 per cent more ammonia accumulated than in the 
normal soil. 

Olaru (1915) states that the nitrogen-fixing power of bacteria from 
legumes is greatly increased by manganese. Gregario (1916) finds that 
mannitol bouillon containing 60 parts per million of manganese in the form 
of the chloride and inoculated with Bacillus radicicola fixes three times as 
much nitrogen as do the checks; a concentration of 200 parts per million 
retards the fixation. Furthermore, he finds that Clostridium pasteur- 
ianum, which normally is not a free fixer, becomes capable of fixing nitrogen 
in the presence of manganese. Similar results have been obtained with 
Azotohacter chroococcwn. 

Summary 

Much of the evidence in the foregoing reports is contradictory. The 
results would be more intelligible if complete data regarding the experi- 
ments were given. The applications of manganese salts to soils have been 
made without any apparent consideration of the type of soil. Such 
factors as soil type, the presence of calcium, and the crop to be grown, 
are factors that determine the action of a given application. Large 
applications on a sandy loam are detrimental, while the same applications 
on a clay loam or on a soil high in calcium would in all probabihty be 
stimulative. 

The role of calcium seems to be a complex one. If the manganese 
were stimulative in the soluble form, the addition of calcium would pre- 
cipitate the manganese and prevent the stimulation. If, on the other 
hand, the manganese were present in such concentration as to be toxic, 
the addition of calcium would be beneficial, not only by causing precipi- 
tation of the manganese but also by increasing the oxidizing power of 
the soil by such precipitation. 

Altho the evidence is in many respects inconclusive, the following 
statements seem to be justified by this review: 

1. Manganese is universally distributed in small quantities in soils and 
plants. 



The Effect of Manganese Compounds on Soils and Plants 379 

2. The majority of experiments indicate that, as Miss Brenchley (1914) 
states, " manganese exerts a toxic influence upon the higher plants, if 
it is presented in high concentration, but, in the absence of great excess 
of the manganese, compounds, the poisoning effect is overshadowed by 
a definite stimulation." 

3. The toxicity of manganese is reduced by nutrient solutions and by soil. 

4. Manganese compounds have been associated with the catalytic 
power of soils and with the oxidizing power of soils and plants. Com- 
paratively large yields have been obtained with manganese fertilization 
under neutral or alkaline soil conditions, and the yields have been cor- 
related with the oxidizing power of the soil. The stimulation of plants 
has in part been explained as due to increased activity in the metabolic 
processes within the leaf. 

5. A stimulation of the ammonification and nitrification in soils has 
also been reported. 

experimental work 

Scope of present study 

In order to test the effect of manganese salts on the growth of plants, 
the weight of wheat seedlings grown in manganese solutions of varying 
concentrations (both in the .presence and in the absence of nutrient salts) 
was compared with the weight of plants grown in cultures containing no 
manganese. The concentrations producing stimulation were then used 
as a basis for the apphcations in the experimental work conducted to 
test the manurial value of manganese when applied to soils. Dunkirk 
silt loam was treated with various manganese salts and planted with 
wheat. An attempt to explain the results obtained led to a study of the 
oxidizing, ammonifying, and nitrifying powers of soils treated with salts 
of manganese. 

Effect of manganese compounds on wheat seedlings grown in water cultures 
Wheat seedlings (Jones' Paris Prize 106^3) from seeds germinated in 
rurming tap water were allowed to attain a growth of about eight centi- 
meters, and were then transferred to culture containers. These were 
salt-mouth bottles of a capacity of 250 cubic centimeters, fitted with 
four-holed corks and wrapped in black paper. Each series was set up 



380 



E. P. Deatrick 



in quadruple and was run for a period of two or four weeks. The nutrient 
solutions were made up from the following formulae: 

Salt 1. Calcium nitrate 27 grams 

Salt 2. Magnesium sulfate 6 grams 

Salt 3. Potassium phosphate (monobasic) 15 grams 

Salt 4, Ferric sulfate 0.5 gram 

Salt 5. Potassium chloride 7.5 grams 

Salts 1 and 5 were dissolved together in 3 liters of water; salt 2 was 
dissolved in 1| Hters, as was also salt 4, and both of these were mixed 
with salts 1 and 5. To the mixture was then added salt 3, after it had 
been dissolved in 3 liters of water. The total quantity was then increased 
to 10 liters by adding 1 liter of water. This solution contains 4656 parts 
per million of salts. 

The wheat seedlings were placed in cultures containing 10, 20, 100, 
200, 400, and 1000 parts per million of manganese in the form of manganese 
sulfate, and were harvested after remaining in the greenhouse for four 
weeks. The results are given in table 1: 

TABLE 1. Wheat Seedlings (Endosperms not Removed) Grown in Solutions of 
Manganese Sulfate. No Nutrients Present 



Parts per million 
of manganese 


Length 
(in centimeters) 


Weight of four plants 
(in grams) 


Total 

dry 

weight 


Relative 
weights 


Leaves 


Roots 


Leaves 


Roots 







11.7 
10.6 
11.5 
10.6 
12.4 
10.9 
9.8 


18.2 
10.3 
5.6 
4.2 
4.6 
3.7 
3.8 


.0784 
.0940 
.0967 
.0658 
.0873 
.0770 
.0641 


.0514 
.0460 
.0319 
.0211 
.0163 
.0222 
.0171 


.1298 
.1400 
.1286 
.0869 
.1036 
.0992 
.0812 


100 


10 


108 


20 


99 


100 


67 


200 


80 


400 


76 


1000 


63 







As shown in table 1, solutions of manganese sulfate containing no nutri- 
ents were found to be toxic. All the manganese cultures, at the termina- 
tion of the experiment, might be characterized as dead or dying. There 
was no great increase in growth, if any increase at all, even in the lowest 
concentration. The total dry matter was reduced in all cases except 
with a concentration of ten parts per million. The first symptom of the 
toxicity of manganese is the yellowing of the tips of the lower leaves. 



The Effect of Manganese Compounds on Soils and Plants 381 



Then bleaching occurs in small patches, which redden, dry, and turn brown. 
The intensity of this chlorotic condition decreases with the decrease in 
the concentration of the manganese. The roots of the plants grown in 
concentrations of 1000 parts per million tui-ned brown in spots, especially 
at the tips, within four days. This browning occurred on the roots 
of .all the plants except the checks, the length of time before the browning 
appeared being proportional to the concentration of the manganese. 

The toxic effect was not so great in cultures of manganese sulfate con- 
taining nutrient salts (4656 parts per million) as in pure solutions, as is 
shown in table 2: 



TABLE 2. 



Manganese Sulfate Added to Nutrient Solutions Containing 4656 Parts 
PER Million op Nutrient Salts 



Parts per million 
of manganese 


Length 
(in centimeters) 


Weight of four plants 
(in grams) 


Total 

dry 

weight 


Relative 
weights 




Leaves 


Roots 


Leaves 


Roots 





19.4 
17.8 
19.2 
21.2 
20.5 
20.7 
16.0 


12.0 
15.4 
15.6 
14.0 
12.8 
9.3 
5.9 


1713 
.2951 
.2668 
.2383 
.2250 
.2020 
.1581 


.0742 
.2033 
.1781 
.1294 
.1052 
.0780 
.0459 


.2455 
.4984 
.4449 
.3677 
.3302 
.2800 
.2040 


100 


10 


203 


20 


181 


100 


150 


200 


135 


400 


114 


1000 


83 



This demonstrates the ameliorating effect of the nutrient salts in over- 
coming or reducing the toxicity of a plant poison. At 1000 parts per 
million the total dry matter was reduced, but it equaled the check at 
400 parts per million and increased with a decrease in the concentration 
of the manganese. The yellowing of the tips of the leaves at 1000 parts 
per million commenced in nine days. The browning of the roots was not 
observed in any of the cultures except those of greatest manganese content. 
A second series of cultures was nm in which the chloride, the carbonate, 
and the dioxide of manganese were used in addition to the sulfate. The 
seedhngs of the first series, reported as having grown in solutions con- 
taining no nutrient salts, were in reality not grown in the absence of other 
elements. That the effect of the stoi'age food in the endosperms is a 
factor in work of this nature, is suggested by McCpol (1913), who states: 

Pea seedlings [cotyledons not removed] that have been grown for ten days in distilled 
water, tap water, and full nutrient solution, respectively, are much more resistant to the 



382 



E. P. Deatrick 



poisonous influence of manganese than those that are transferred from germinating pans 
and placed immediately in solutions of manganese. The nature of the medium used in this 
preliminary treatment — that is, whether distilled water, tap water, or full nutrient solution — 
has no visible effect on the resisting power of the plants." 

The seeds in this second series, consequently, were germinated as before, 
but when the seedHngs were about eight centimeters high the endosperms 
were pinched off. This was done to eUminate as much as possible the 
influence of the storage food. The concentration of the nutrient solution 
was but one-fifth of that used in the previous series of cultures. 

The average dry weight of the wheat seedlings at the time of setting 
up the cultures was determined, so that the effect of the manganese solu- 
tions might be the more accurately ascertained. The results are given 
in tables 3 and 4 : 



TABLE 3. 



Wheat Seedlings (Endosperms Removed) Grown in Solutions of 

Manganese Salts. No Nutrients Present 



Parts per million of manganese 


Average 

dry weight 

(grams) 


Increase 

or decrease 

in weight 

during the 

two weeks 

(grams) 


Relative 
increase or 
decrease in 

weights 





.0319 


.0025 


100 



Manganese sulfate 



1. 

5. 

10 

100. 

1000. 




168 
40 
16 
60 

-144 



Manganese chloride 



1. 
5. 

10. 

100. 

1000. 




232 

192 

152 

60 

-168 



Manganese carbonate 



1. 

5. 

10. 

100 




112 

224 

12 

220 



The Effect of Manganese Compounds on Soils and Plants 383 



TABLE 4. 



Manganese Salts Added to Nutrient Solutions Containing 961 Parts 
PER Million of Nutrient Salts 









Increase 








Average 


in weight 


Relative 




Parts per million of manganese 


dry weight 


during the 


mcrease m 






(grams) 


two weeks 
(grams) 


weights 


0.. 




0367 


.0073 


100 



Manganese sulfate 



1, 

5. 

10. 

100 

1000. 



0098 


134 


0110 


151 


0129 


177 


0106 


145 


0066 


90 


0091 


125 


0125 


171 


0101 


138 


0093 


127 


0026 


36 



Manganese chloride 



1. 

5. 

10. 

100. 

1000. 



Manganese carbonate 



1 


.0367 
.0376 
.0387 
.0455 


.0073 
.0082 
.0093 
.0161 


100 


5 


112 


10 


127 


50 


220 







It will be noticed that by this procedure it has been possible to show 
an actual decrease in the weight of the seedlings grown in the solutions 
of highest concentrations of the sulfate and the chloride. 

An examination of tables 3 and 4, giving the results of this series of 
experiments, shows that these results agree in general with those of the 
first series; that is, as the concentration of the manganese decreases, the 
total dry weight increases. The figures show clearly the greater toxic 
effect of the manganese in the absence of the endosperm. The results 
here reported agree closely with those of Miss Brenchley (1914). 

Effect of manganese compounds on wheat grown in soil 
The determination of the effect of a given factor when added to the 
soil is complex. The effect of this factor on the growth of plants is but 



384 



E. P. Deatrick 



an indication of its resultant effect on the various activities in a complex 
medium. It was therefore deemed advisable to detei-mine, in the first 
place, whether the addition of manganese sulfate to soil cultures inhibits 
its power to function as in the case of water cultures. Consequently, 
wheat was grown on soil to which manganese sulfate had been added in 
varying amounts. 

In this, as well as in other soil experiments, the soil used was Dunkirk 
silt loam, obtained near the experimental plats of Caldwell Field. The 
results of the chemical and mechanical analyses are given in tables 5 
and 6, respectively: 

TABLE 5. Chemicai, (Bulk) Analysis of Dunkirk Silt Loam 



Constituent determined 



Surface 

1 to 12 inches 

(per cent) 



Subsoil 

12 to 24 inches 

(per cent) 



Nitrogen (N) 

Organic carbon (C) 

Carbon dioxide (CO2) 

Calcium oxide (CaO) 

Magnesium oxide (MgO) . . . 

Potassium oxide (K2O) 

Sodium oxide (Na.;0) 

Phosphoric anhydride (P2O0) 
Manganese oxide (Mni04).. . 



186 
1.670 
Trace 
0.430 
0.450 
1.740 
1.090 
0.123 




0.082 
0.440 
0.260 
0.830 
0.690 
2.110 
1.280 
0.126 




TABLE 6. Mechanical Analysis of Dunkirk Silt Loam 



Fine gravel . . . 
Coarse sand . . 
Medium sand. 
Fine sand .... 
Very fine sand 

Silt 

Clay 



Per cent 
0.5 
0.8 
'O'.B 
2.7 
9.5 
67.3 
18.6 



The soil was procured in quantity, was allowed to partially dry out in 
the air, and was then passed thru a 2-millimeter sieve. After treatment 
with manganese sulfate the soil was placed in small wire baskets, 350 



The Effect of Manganese Compounds on Soils and Plants 385 

grams to a basket. The baskets were paraffined and a sand mulch was 
placed on the surface. Six baskets of each treatment were set up, four 
of which were planted with wheat seedlings about 10 centimeters high. 
There were four seedlings in each basket. The baskets were carried to 
the greenhouse, where they remained for a period of three months. Dur- 
ing that period they received such applications of distilled water, from 
time to time, as would bring the soil up to the original moisture content 
of 25 per cent (dry basis). On May 3, 1916, the crop was harvested, 
and the plants were dried, weighed, and analyzed for manganese. The 
results are given in table 7 : 

TABLE 7. Wheat Grown for Three Months on Dunkirk Silt Loam Treated with 

Manganese Sulfate 



Parts per million of manganese added 


Average weight 

of seedhngs 

in each culture 

(grams) 


Relative 
weights 


. ... 


2.70 
3.25 
2.80 
1.94 
2.05 


100 


10 


120 


50 


104 


100 : 


72 


1000 


76 







An examination of the relative weights shows that the manganese is 
at least not prevented entirely from stimulating plant growth when it 
is added to soil. The stimulation at 10 parts per million was appre- 
ciable. 

Another set of cultures was arranged on December 12, 1916. Two kilo- 
grams of air-dry soil, to which the various quantities of manganese sulfate 
were added, was placed in wire baskets. These ba,skets then received a 
coating of paraffin and a sand mulch. Seven of the baskets received an 
appUcation of calcium carbonate at the rate of 20,000 parts of CaO per 
million of soil. The soil was seeded to wheat and the moisture content 
was raised to 25 per cent (dry basis), where it was kept by the addition 
of distilled water from time to time. One month later the seedlings were 
thinned to five to a basket, and these were allowed to grow for seven and 



386 



E. P. Deatrick 



one-half months. The crop was harvested on July 3, 1917. The yields 
obtained are recorded in tables 8 and 9: 

TABLE 8. Wheat Grown for Seven and One-Half Months on Dunkirk Silt Loam 
Treated with Manganese Sulfate 



Parts per million of manganese added 


Weight of straw 


Weight of grain 


Average 

(grams) 


Relative 


Average 

(grams) 


Relative 





5 6 

5.0 

5.7 

• 3.5 


100 
89 

102 
62 


2.0 
4.0 
4.1 
2.3 


100 


10 


200 


25 


205 


50 


115 







TABLE 9. Wheat Grown for Seven and One-Half Months on Dunkirk Silt Loam 
Treated with Manganese Sulfate and 20,000 Parts per Million of Calcium Car- 
bonate 





Weight of straw 


Weight of grain 


Parts per million of manganese added 


Average 

(grams) 


Relative 


Average 

(grams) 


Relative 





1.7 
4.5 
4.9 
5.0 


100 
265 
288 
294 


1.7 
2.0 
1.8 
2.1 


100 


10 


118 


25 


106 


50 


123 







The effect of the manganese in these cultm-es is not apparent when 
the yields are considered. Practically all the yields of the soil treated 
with manganese are somewhat higher than those treated with calcium. 
The yield for the calcium carbonate check is strikingly low, for which no 
reason can be assigned by the writer. Greater differences, however, than 
those that appear in the data of table 9, were noted at an earlier stage 
of growth. It was observed that a majority of the manganese plants 
headed before the calcium-manganese plants did. In this respect it 
would seem that the calcium had interfered with the action of the 
manganese. 



The Effect of Manganese Compounds on Soils and Plants 387 

Other investigators have stated that the effect of manganese on yield 
is not marked. While Bertrand (1909) notes that the favorable results 
of manganese are not apparent until harvest time, Miss Brenchley 
(1914) states that there is a retarding effect on the ripening of the grain 
but not on the yield. Takeuchi (1909-13) reports that the control plants 
of flax were behind the manganese plants in growth and flowering. Aso 
(1904-05) found that rice treated with manganese flowered four days earlier 
than did the checks. Salomone (1907) states that the stimulation of the 
vegetative portion of plants is greater than that of the grain. Comparison 
of the data in tables 7 and 8 shows that greater differences in the yields 
were obtained when the plants were harvested before they matured. 

Manganese content of yellow leaves 

Several investigators have reported that the yellow leaves of manganese 
plants contain more manganese than do the green leaves. The leaves of 
the plants grown on soil treated with manganese sulfate (page 385) were 
analyzed for their manganese content by the colorimetric method described 
in Bulletin 31 of the United States Bureau of Soils. The results are given 
in table 10: 



TABLE 10. 



Analyses of Leaves of Wheat Grown on Soil Treated with Manganese 
Sulfate 



Parts per million of manganese added 


Manganese (in parts per million grams 
of dry matter) in 


Green 

leaves 


YeUow 
leaves 


Medium 
yellow 
leaves 




10 

50 


Trace 

Trace 

Trace 

1.15 

1.95 


Trace 

Trace 

3.8 

7.25 

11.25 


Trace 

Trace 

1.22 


100 

1000 


3.37 
3.12 



If Aso (1902-03) is correct in stating that the colorimetric tests for the 
oxidizing enzymes showed that " the yellowish leaves of the manganese 
plants gave reactions of higher intensity than the green leaves of the control 
plants," it seems that the intensity of these enzymes is proportional to 



388 E. P. Deatrick 

the manganese content of the leaves. Woods (1899) states: " It has 
long been known that chlorophyll could be readily converted by oxida- 
tion, into a yellow coloring matter, xanthophyll." While a moderate 
stimulation of the oxidizing power of the plant juices may result bene- 
ficially, an excessive stimulation may result in the oxidation of the chloro- 
phyll. 

Relation of manganese to the oxidizing power of soils 

In some cases the lack of fertility in a soil has been shown to be due to 
the presence of certain organic substances injurious to plant growth. 
Schreiner and Shorey (1909) found that when such soils are well aerated 
they become productive. Schreiner, Sullivan, and Reid (1910:44) state 
that the addition of manganese to soils promotes " the most active oxi- 
dation," and " by its strong oxidizing power would render the 

injurious material in the soil harmless or even beneficial and by the oxi- 
dation of inert or rather stable organic matter might cause" a liberation 
of plant food. A brief study of the effect of manganese salts on the oxi- 
dizing power of soils has therefore been made by the writer. 

Portions of Dunkirk silt loam were sprayed with solutions of manganese 
chloride, manganese sulfate, potassium permanganate and suspensions of 
manganese carbonate, and manganese dioxide, in quantities such that 
the manganese added was in the proportion of 10, 100, and 1000 parts 
of manganese per million of dry soil. It was thought that by spraying 
the soil a more uniform distribvition of the manganese could be obtained. 
Consequently the calculated amounts of the salts were added to sufficient 
water to bring the soil to 25 per cent moisture content (dry basis). The 
spraying was done with a simple atomizer, made with two pieces of glass 
tubing of different bore and a wide-mouth bottle. It was found that the 
physical condition of the soil was very good when the water was added 
in this way. A determination showed that the moisture lost in the form 
of mist and evaporation during the treatment was negligible. The soils 
were stored in glass quart jars for about seven months. 

To test the oxidation in the soil, 50 cubic centimeters of the following 
solution was added to 10 grams of the air-dried soil in a centrifuge tube: 
10 grams aloin 
200 cubic centimeters N/lO HCL 
790 cubic centimeters distilled water 



The Effect of Manganese Compounds on Soils and Plants 389 

The tube was shaken for exactly one-half minute and was then placed in 
the centrifuge, which was started one minute after the solution was added. 
At the end of two minutes the electric current was turned off the centrifuge, 
and the speed was allowed to decrease gradually while a second test was 
started. Five minutes after the aloin was added in the first test, a 
portion of the supernatant liquid was poured ijito a colorimeter tube 
and the depth of color was compared with that of a standard. 

This method will be found to differ considerably from that of Schreiner, 
Sullivan, and Reid (1910). The oxidation in the soils reported was so 
great that it was found necessary to use the method already described. 
The difference between the two methods is indicated by the following: 





Schreiner, 
Sullivan, 
and Reid 


Deatrick 


Time of test 


2 to 3 hours 
0. 125 per cent 
C2H5OH 


5 minutes 


Concentration of aloin solution 

Flocculating agent 


1 . per cent 
HCL 







The standard used in the writer's experiments was a solution of aloin 
which had been completely oxidized with either manganese dioxide or 
nitric acid. The results were calculated on the basis of the oxidation in 
the untreated soil as 100. 

The oxidation of phenolphthalin (made by reducing phenolphthalein 
with zinc dust and sodium hydroxide) was also used as a means of testing 
the oxidation in soils. The data are given in table 11. These figures 
indicate definitely that the addition of manganese salts to soils increases 
the power to oxidize organic matter such as aloin and phenolphthalin. 
It appears that the salts which are the most effective are the perman- 
ganate, the chloride, and the sulfate. 

While the treatment with manganese dioxide seems to have interfered 
slightly with oxidation, it has been observed that soils treated with pre- 
cipitated manganese oxides, instead of the pulverized pyrolusite, oxidize 
aloin readily. The oxidation in the air-dry soil from the field was very 
weak. The increase due to the moisture treatment alone is very noticeable. 
Since the soil contains no manganese, this is due to some other cause. 



390 



E. P. Deatrick 



TABLE 11. Oxidation _iN Dunkirk Silt Loam Treated with Manganese Salts 
(Tests made seven months after treatment) 





Parts per million of manganese added 


Relative 


oxidation 






Aloin 


Phenolphthalin 





100 




100 






Potassium permanganate 

1 




10 


101 
136 
444 




100 


100 


120 


1000 


200 






Manganese dioxide 




10 


93 
94 
95 




100 


100 


100 


1000 


100 






Manganese chloride 




10 


105 
113 
171 




100 


100 


125 


1000 


167 






Manganese carbonate 






10 


105 
117 
128 




100 


100 . 


100 


1000 


142 






Manganese sulfate 




10 


105 
136 
233 




100 


100 


130 


1000 


172 







Adsorption of manganese 
It had been noted that soil to which manganese salts were added devel- 
oped a power to oxidize aloin in proportion to the length of time that 
the salt was in contact with the soil. In order to test this more accurately, 
portions of soil, the moisture content of which had been held at 25 per 
cent for seven months, were treated with solutions of manganese sulfate. 
The data, given in table 12, indicate that oxidation does not develop at 
once, but that it is greatest in the soil in which the manganese has been 
present for the longest time. 



The Effect of Manganese Compounds on Soils and Plants 391 



TABLE 12. Effect of Duration of Contact of Soil with Manganese Sulfate, on 
THE Oxidizing Power of the Soil 



Parts per million of 
manganese added 



10 

10 

1000 

1000 



Date when 

manganese was 

added 



April 3, 1916 
November 8, 1916 
April 3, 1916 
November 8, 1916 



Date when 

oxidation was 

determined 



November 8, 1916 
November 8, 1916 
November 8, 1916 
November 8, 1916 



Relative 
oxidation 



100 
100 
185 
112 



In order to test the adsorptive power for manganese, four percolation 
cylinders were filled with Dunkirk silt loam, a kilogram to each cyhnder. 
The cyHnd'ers were labeled A, B, C, and D, respectively. To soils C 
and D calcium hydroxide was added at the rate of 10,000 parts of CaO 
per milhon of soil. Soils A and B were untreated. A solution of 
manganese sulfate containing 1000 parts per milhon of manganese was 
then percolated thru the soils after they had been saturated with distilled 
water. Each successive 100 cubic centimeters of the percolate was 
analyzed for manganese by the colorimetric method described in Bulletin 31 
of the United States Bureau of Soils. The manganese content of the 
percolates, expressed in parts per million, is given in table 13: 



TABLE 13. Manganese Content of Manganese Sulfate Solution (1000 Parts per 
Million of Manganese) Percolated thru Dunkirk Silt Loam 





Successive 100-cc. portions 
of percolate 


Manganese content 


in parts per 


million 




A 


B 


C 


D 


1 



Trace 
62 
500 
625 
715 
715 
715 
715 
770 



111 
286 
400 
417 
455 
500 
525 
555 
475 








Trace 

62 

154 

218 

256 

357 

357 





2 





4 





6 





8 ... 


Trace 


10 


92 


12 


167 


14 


143 


16 


222 


18 


91 







392 E. P. Deatrick 

The soils treated with calcium hydroxide precipitated more manganese 
than did the untreated soils. In the case of soil C, one Uter of the solution 
was passed thru it before any appreciable amount of manganese appeared 
in the percolate. On air-drying these soils, C and D were found to have 
an intensive oxidizing power as compared with A and B. 

Soils treated with 1000 parts per million of manganese in the form of 
pulverized pjrrolusite were found not to have a strong oxidizing power. 
A solution of aloin, however, is rapidly oxidized when some of the pyrolusite 
is added to it. Colloidal manganese dioxide (from potassium permanganate 
and hydrochloric acid, purified by decantation) oxidizes aloin immediately. 
These phenomena, added to the fact that soils C and D developed the 
oxidizing power immediately in the presence of calcium, have led the 
writer to believe that the oxidation in soils due to manganese is due to 
the presence of manganese dioxide. In a solution of a manganese salt, 
manganic hydroxide is readily formed on the addition of an alkali. The 
formation of the oxide in soil to which a soluble manganese salt has been 
added, is directly proportional to the Hme content, that is, the basicity 
of the soil. In the absence of an excess of an alkali form of calcium, 
the formation of the oxide of manganese is slower, for the stability of the 
soluble salts, as the sulfate and the chloride, is of course greatest in an 
acid solution. The salts of the weak acids, however, are not so stable, 
and when adsorption phenomena play a part, the salts are unstable even 
in neutral media. Thus, if pure, fine sand is treated with a solution of 
manganese citrate, this instability is soon demonstrated by the browning 
of the sand. This has been found to be the case with sand so treated 
and stored in a jar. On exposure to air, sand treated with the acetate 
and the citrate has developed a slight brown color. 

Schreiner, Sullivan, and Reid (1910) apparently tested their soils 
immediately after adding the manganese salts. These soils were prob- 
ably deficient in lime, and therefore the addition of manganese did not 
increase oxidation. The increase noted when hydroxy acids were added 
to these soils may have been due to the formation of the organic salt of 
manganese and the subsequent precipitation of the oxide from the less 
stable salt. 

The formation of the dioxide, and the oxidation phenomena in soils 
as described, are analogous to the formation of calcium manganite (CaO. 



The Effect of Manganese Compounds on Soils and Plants 393 

Mn02) and its use in the Weldon recovery process for the preparation of 
chlorine. The mixture of milk of lime and manganese chloride is termed 
Weldon, or manganese, mud. 

Oxidation by plant roots 

That roots of plants have an extracellular oxidizing power " may be 
demonstrated by the use of suitable chromogens," according to Schreiner 
and Reed (1909). In regard to their work on root oxidation in culture 
solutions containing alpha-naphthylamine, these investigators state (page 
17 of reference cited) that " when the oxidation is performed by the grow- 
ing roots of a plant, the oxynaphthylamine is deposited uf)on the sin-face 

of the roots in characteristic zones The zone of primary meris- 

tematic cells immediately back of the root cap is marked by a distinct 
narrow band of color." The browning of the roots of wheat in solutions 
of manganese salts resembles the staining caused by the oxidation of alpha- 
naphthylamine. 

The reports of investigators indicate that such browning is character- 
istic of plants other than wheat, when grown in manganese solutions. 
This browning has been reported as consisting of a deposit of manganese 
dioxide. As far as can be ascertained by the writer, no proof has been 
offered for this statement. That the dioxide is formed, however, is indi- 
cated by the following: The black deposit is insoluble in water but 
dissolves in hydrochloric acid. When this solution is evaporated and the 
residue is fused with an alkali carbonate on platinum foil, the character- 
istic green color of the alkali manganate is developed. Furthermore, 
the blackened roots are capable of liberating chlorine from a solution of 
a chloride and sulfuric acid. If the plants thrive long enough in the man- 
ganese solution, the whole root system becomes blackened. 

In writing of the deposit of manganese dioxide. Miss Houtermans (1912) 
states that the blackening is probably the result of enzymotic processes. 
The browning is the result of the oxidation which occurs on the surface of 
the root. The fixed alkali hydroxides precipitate from solutions of man- 
ganese salts manganous hydroxide, white, which readily turns to brown 
manganic hydroxide in the air or in contact with other oxidizing agents. 
Since manganous hydroxide is formed in the solution of a manganese 
salt by hydrolysis, it seems that it is deposited on the roots, as such, and 



394 



E. P. Deatrick 



is there oxidized to a higher oxide, as the insoluble brown deposit. Soon 
after the heavy deposition of the oxide, disintegration of the root occurs. 

Schreiner and Reed (1909) conclude that "the process of oxidation by 
roots is largely, if not entirely, due to the activity of a peroxidase produced 
by the roots." That the deposit is not caused merely by the instability 
of the manganese solutions in the presence of organic matter is indicated 
by the absence of any blackening on pieces of string or wood placed in 
them. A definite relation has been established between stimulants of 
this oxidizing power and stimulants of growth. Schreiner, Sullivan, and 
Reid (1910:9) state that " oxidation by plant roots is a factor which 
has considerable agricultural interest, especially from the viewpoint that 
such oxidation is able to change the organic matter in the medium in 
which the plant is growing and that processes promoting oxidation play 
a large part in the best methods of soil cultivation." 

The effect of manganese on the oxidizing power of the roots of wheat 
seedlings was therefore investigated. Seedlings were set up as before in 
nutrient solutions (931 parts per million of salts) and grown for two weeks. 
Portions of these solutions were then treated with small quantities of the 
aloin solution and allowed to stand for twenty-four hours, and a com- 
parison was then made of their relative oxidation. The results appear in 
table 14: 

TABLE 14. Effect of Manganese Sulfate on Oxidation by Roots 





Parts per million of manganese 


Oxidation 


n solutions 




With 

plants 


Without 
plants 





100 
184 
191 
181 
244 
250 
206 





1 





5 





10 





50 





100 , 





1000 


167 







In every case the cultures in which plants had grown oxidized the aloin 
more than did those in which no plants were grown. In fact, the aloin 
was but faintly oxidized in the checks, and with the exception of the one 
containing the greatest quantity of manganese the degree of oxidation 



The Effect of Manganese Compounds on Soils and Plants 395 

was considered as zero. When phenolphthalin was used as an indicator 
similar results were obtained, altho some trouble was experienced with 
these solutions because of the carbon dioxide content. 

The bluing of gum guaiac was also used as an indication of the oxidizing 
power of the roots. The reagent, which was poured on the surface of the 
cultures, followed the path of the roots where it was oxidized. The 
objection has been raised that due consideration was not given to the 
oxidizing power of the manganese sulfate. It was found that a solution 
of gum guaiac is oxidized immediately by a solution of manganese sulfate 
containing approximately 10,000 parts per million of manganese. A 
solution of 1000 parts per million, however, gave only a slight bluing 
after three hours. Immediate bluing was obtained by the roots of plants 
grown in the presence of 10 parts per million of manganese in the form 
of the sulfate, while the bluing by the roots of the check plants was slow 
and not so intense. 

Effect of manganese sulfate on soil bacteria 

Numerous investigators have reported that the activity of the lower 
forms of plant life is increased by the presence of manganese salts. In 
order to test this point, cultures were set up to determine the effect of 
manganese sulfate on the ammonification of dried blood and the nitrifica- 
tion of ammonium sulfate in soil. These cultures were prepared from a 
fresh stock of Dunkirk silt loam, which had been passed thru a two- 
millimeter sieve and which contained 12 per cent (dry basis) of water. 
Portions of the soil each weighing 112 grams were placed in eight-ounce 
salt-mouth bottles. When properly treated the cultures were placed on 
the laboratory desk and covered with a moist pad, made of cheesecloth 
and cotton, to prevent the evaporation of water. It was found that in 
this way a large number of cultures could be kept at a constant moisture 
content with the expenditure of a minimum amount of labor. The 
cultures were run in quadruplicate and were incubated at room temper- 
ature. Two days after the cultures were set up, the soil in each bottle 
was stirred so as to insure uniformity in the distribution of the salts added. 
At the end of the incubation period, the soil in each bottle was stirred 
with 475 cubic centimeters of distilled water for three minutes and then 
allowed to settle for twenty minutes, and the supernatant Uquid was 
filtered thru a Pasteur-Chamberlain filter. AHquot portions of the filtrate 
were then analyzed for ammonia and nitrates. The ammonia was deter- 



396 



E. P. Deatrick 



mined b}^ adding concentrated sodium hydroxide, distilling, and titrating 
the distillate with tenth-normal hydrochloric acid. The nitrates were 
determined by the phenol-disiilfonic-acid method, using the Schreiner 
colorimeter to read the intensity of color. 

Ammonification. — To the soil used for ammonification tests was first 
added 0.5 per cent of dried blood. The manganese sulfate was added 
after the soil had been weighed out and placed in the culture bottles. 
Sufficient water was used as the solvent of the manganese sulfate to bring 
the soil in each culture to a moisture content of 25 per cent (dry basis). 
The cultures were incubated for one week, at the end of which extracts 
and determinations were made as described above. The results are given 
in tables 15 and 16: 

TABLE 15. Effect of Manganese Sulfate on Ammonification of Dhied Blood in 

Dunkirk Silt Loam 

(Cultures incubated for seven days) 



Parts per million of manganese added 


Nitrogen 

as ammonia, 

average of 

4 cultures 

(milligrams) 


Relative 
amounts 





34 

47 
53 
47 
54 
58 
67 


100 


10 


138 


20 


156 


30 


138 


50 


159 


70 


170 


100 


197 







TABLE 16. Effect of Manganese Sulfate and 20,000 Parts per Million of Calcium 
Carbonate on Ammonification of Dried Blood in Dunkirk Silt Loam 





(Cultures incubated for seven days) 






Parts per million of manganese added 


Nitrogen 

as ammonia, 

average of 

4 cultures 

(milligrams) 


Relative 
amounts 





87 

96 

109 


100 


100 


110 


1000 


125 







The Effect of Manganese Compounds on Soils and Plants 397 

The addition of manganese sulfate to the soil resulted in a positive 
stimulation in the ammonifying power. The addition of calcium car- 
bonate resulted in a greater stimulation than that caused by the manga- 
nese alone. The stimulation of the manganese is not so great in alkaline 
soil as in soil deficient in calcium. This is as would be expected, for the 
solubility of the manganese is decreased. 

Nitrification. — To the soil used for nitrification tests, 220 parts per 
million of nitrogen in the form of ammonium sulfate was added. The 
calculated quantities of solutions of manganese and ammonium sulfate 
were mixed, and were added to the soil in the culture bottles together 
with sufficient water to bring the soil to a moisture content of 25 per cent 
(dry basis). The cultures were incubated for four weeks. At the end 
of this time the extracts and determinations were made as described, 
and the results, expressed as parts of nitrates per million parts of dry 
soil, are given in tables 17 and 18. The experimental error of this deter- 

TABLE 17. Effect of Manganese Sulfate on Nitrification of Ammonium Sulfate 

IN Dunkirk Silt Loam 

(Cultures incubated for thirty days) 



Parts per million of manganese added 


Nitrates, 
average of 
4 cultures 
(parts per 
million 

of soil) 


Relative 
amounts 





234 
236 
252 
197 
156 
136 
122 


100 


10 


101 


20 


108 


30 . . 


84 


50 


67 


70 


58 


100 


52 







mination is large, and the data given in the tables indicate that manganese 
sulfate in low concentrations did not affect the nitrifying power of the 
soil. In soils containing larger amounts of manganese, however, the 
nitrification was checked. 



398 



E. P. Deatrick 



TABLE 18. Effect of Manganese Sulfate and 20,000 Parts per Million of Calcium 
Carbonate on Nitrification of Ammonium Sulfate in Dunkirk Silt Loam 

(Cultures incubated for thirty days) 







Nitrates, 






Parts per million of manganese added 


average of 

4 cultures 

(parts per 

million 

of soil) 


Relative 
amounts 





344 
326 
273 


100 


100 


95 


1000 


79 


• 







Conclusions 

The experimental data here reported seem to justify the following 
conclusions : 

1. Manganese salts added to water cultures affect the growth of wheat 
seedlings. The comparison of relative weights shows that when presented 
to the plant in high concentrations, both the sulfate and the chloride 
exert a toxic effect. In lower concentrations, manganese causes a marked 
stimulation. 

2. The degree of toxicity is reduced by full nutrient solutions and the 
reduction is directly proportional to the concentration of the nutrient 
salts. Likewise, the food stored in the endosperms reduces the toxicity 
of the plant poison. 

3. The toxic influence results in the browning of the roots and the 
bleaching of the leaves. The yellow leaves of the manganese plants 
contain more manganese than do the green ones. 

4. Manganese salts added to soil form manganese dioxide in proportion 
to the basicity of the soil, and thus develop a power to oxidize organic 
matter as shown by the oxidation of aloin or phenolphthalin. 

5. Manganese sulfate in water cultures stimulates the oxidizing power 
of the roots of wheat seedUngs. 

6. Low concentrations of manganese sulfate were found to stimulate 
the ammonification of dried blood in soil. The nitrification of ammonium 
sulfate was inhibited. 



The Effect of Manganese Compounds on Soils and Plants 399 



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Memoir 17, The Translocation of Calcium in a Soil, the second preceding number in this series of 
publications, was mailed on February 12, 1919. 



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